CN103183853B - Tire belt laminating rubber combination and the tire utilizing said composition to manufacture - Google Patents
Tire belt laminating rubber combination and the tire utilizing said composition to manufacture Download PDFInfo
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- CN103183853B CN103183853B CN201210570424.2A CN201210570424A CN103183853B CN 103183853 B CN103183853 B CN 103183853B CN 201210570424 A CN201210570424 A CN 201210570424A CN 103183853 B CN103183853 B CN 103183853B
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- BKADZRJXLYXJNF-UHFFFAOYSA-N C/S=C(\N1CCCC1)/[Sm]C(N1CCCC1)=S Chemical compound C/S=C(\N1CCCC1)/[Sm]C(N1CCCC1)=S BKADZRJXLYXJNF-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/06—Polysulfones; Polyethersulfones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Tires In General (AREA)
Abstract
The tire that the present invention relates to tire belt laminating rubber combination and utilize said composition to manufacture, comprises: the crude rubber of 100 weight parts; The aromatic polyamide staple fibre particle of 0.01 to 10 weight part, it is formed by the aromatic polyamide staple fibre conjunction sth. made by twisting of more than 2 strands, and comprises the rubber permeated between the aromatic polyamide staple fibre of described twisting.Described tire belt laminating rubber combination can improve the rigidity of belt laminating rubber, reduces coating thickness, reduces the lag-effect of described belt laminating rubber, thus the power loss occurred when can reduce tire rotation.
Description
Technical field
The tire that the present invention relates to tire belt laminating (belt topping) rubber combination and utilize said composition to manufacture, particularly, relate to the rigidity improving belt laminating rubber, reduce coating thickness (topping gauge), reduce the lag-effect of described belt laminating rubber, thus the tire belt laminating rubber combination of the power loss occurred when can reduce tire rotation and the tire that utilizes said composition to manufacture.
Background technology
Usually, the middle portion in radial between carcass to tyre surface is called belt, the materials'use organism of this belt and steel cord.
Described belt is arranged to connect rotund angle at tire outside left, forms by solid multiple band bundle cord overlaps of laminating rubber laminating.Described belt as strength layer, is very important position in radial.
The steel cord forming described belt is divided into, and twists with the fingers the tight multiply cord forming steel cord with the multiply filament that diameter is very little; The sub-thread cord of steel cord is formed with one filament large with diameter.Multiply filament closes the steel cord twisted with the fingers and formed, and the rubber of its laminating permeates between the gap of the steel cord of twisting, and the bonding force of therefore fitting between rubber and steel cord is good, and the steel cord that sub-thread is formed has the relatively low shortcoming of bonding force between rubber.
Described steel cord and and the rubber of its laminating between the weather resistance of bonding force to tire have a huge impact.Actually by be applied to tire load repeatedly and cause steel cord and around steel cord laminating rubber between bonding force die down, and the breakage carrying out tire is started with the form in crack, this crack becomes the stripping causing greatly steel cord and laminating rubber gradually, is one of important factor causing vehicle safety accident.
In addition, in order to improve the braking ability of tire, be necessary to reduce the heat occurred between tire and road surface and the power loss caused.For this reason, reduce the rubber content forming tire, thus the lag-effect occurred in minimizing rubber seems important.The method reducing the content of the rubber forming described tire has the coating thickness reducing belt.
But, when reducing the coating thickness of belt, the problem that the combination between steel cord and laminating rubber dies down cannot be avoided.
Prior art document
Patent documentation
No. 2004-0043538, KR published patent (publication date: on April 24th, 2004)
No. 2006-0134483, KR published patent (publication date: on December 28th, 2006)
No. 2007-0000860, KR published patent (publication date: on January 3rd, 2007)
No. 2007-0095546, KR published patent (publication date: on October 1st, 2007)
Summary of the invention
The object of the present invention is to provide a kind of rigidity improving belt laminating rubber, reduce coating thickness, reduce the lag-effect of described belt laminating rubber thus, thus the tire belt laminating rubber combination of the power loss occurred when can reduce tire rotation.
Another object of the present invention is to provide the tire utilizing described tire belt laminating rubber combination to manufacture.
In order to achieve the above object, tire belt laminating rubber combination comprises according to an embodiment of the invention: the crude rubber of 100 weight parts; The aromatic polyamide staple fibre particle of 0.01 to 10 weight part, it is formed by the aromatic polyamide staple fibre conjunction sth. made by twisting of more than 2 strands, and comprises the rubber of infiltration between the described aromatic polyamide staple fibre of twisting.
Described aromatic polyamide staple fibre can use the compound or its hydrate that are represented by following chemical formula 1 and polysulfide to carry out surface treatment.
[chemical formula 1]
In above-mentioned chemical formula 1, described Me is basic metal, and described n is the integer of 1 to 10, and described m is the integer of 1 to 6.
Described polysulfide is selected from the one in the compound of following chemical formula 2 to 6 expression.
[chemical formula 2]
[chemical formula 3]
[chemical formula 4]
[chemical formula 5]
[chemical formula 6]
In above-mentioned chemical formula 2 to 6, described R
1and R
2be selected from the one in the aralkyl of hydrogen, halogen, nitro, hydroxyl, the alkyl of carbonatoms 1 to 12, the alkoxyl group of carbonatoms 1 to 12 and carbonatoms 1 to 12 independently of one another, described m is the integer of 1 to 6.
Described aromatic polyamide staple fibre can be mean length is 1 to 10mm, mean diameter is 0.01 to 1.0mm.
Described aromatic polyamide staple fibre Particle Phase, for the described aromatic polyamide staple fibre of 100 weight parts, comprises the rubber of the described infiltration of 10 to 50 weight parts.
Described tire belt laminating rubber combination can comprise N2 adsorption specific surface area (nitrogen surface area per gram, N further
2sA) be 100 to 200m
2/ g, CTAB (cetyl trimethylammonium bromide) adsorption specific surface area is 100 to 200m
2silicon-dioxide 20 to 90 weight part of/g.
Tire utilizes described tire belt laminating rubber combination to manufacture according to another embodiment of the present invention.
Below, the present invention is further described.
Comprise 100 raw material rubber according to the tire belt laminating rubber combination of one embodiment of the invention and formed by the aromatic polyamide staple fibre conjunction sth. made by twisting of more than 2 strands, and comprising 0.01 to 10 parts by weight of aromatic polyamide short fibre particle of the rubber of infiltration between the described aromatic polyamide staple fibre of twisting.
Described crude rubber can be selected from the one selected in natural rubber, synthetic rubber and their combination.
Described natural rubber can be common natural rubber or modified natural rubber.
As long as the natural rubber that described common natural rubber is known all can use, not by the restriction in country of origin etc.Although cis-Isosorbide-5-Nitrae-polyisoprene comprises as main body by described natural rubber, characteristic as requested can comprise anti-form-1,4-polyisoprene.Therefore, except with cis-1 in described natural rubber, 4-polyisoprene is outside the natural rubber that comprises of main body, can also comprise a kind of balata etc. producing Sapotaceae rubber in such as South America and comprise anti-form-1 as main body, the natural rubber of 4-polyisoprene.
Described modified natural rubber refers to that described common natural rubber is through modification or refining.Such as, the example of described modified natural rubber has epoxy natural rubber (ENR), DPNR (DPNR), HNR hydrogenated natural rubber etc.
Described synthetic rubber is selected from styrene butadiene rubbers (SBR), modified styrene-butadiene's rubber, divinyl rubber (BR), modified butadiene rubber, chlorosulfonated polyethylene rubber, epichloro hydrin rubber, viton, silicone rubber, paracril, hydrogenated nitrile-butadiene rubber, nitrile butadiene rubber (NBR), modification nitrile butadiene rubber, polyvinyl chloride rubber, styrene-ethylene-butylene-styrene (SEBS) rubber, ethylene propylene rubber, Ethylene Propylene Terpolymer (EPDM) rubber, chlorosulfonated polyethylene rubber, neoprene, ethylene vinyl acetate rubber, acrylic elastomer, propylene dichloride rubber, Benzyl Chloride styrene butadiene rubbers, bromomethylstyrene isoprene-isobutylene rubber, maleic acid styrene-divinyl rubber, carboxylic acid styrene butadiene rubbers, epoxy synthetic polyisoprene, maleat acrylic rubber, carboxylic acid nitrile butadiene rubber, bromination gathers the one in isobutyl-isoprene-altogether-p-methylstyrene (brominated polyisobutyl isoprene-co-paramethyl styrene, BIMS) and their combination.
Described aromatic polyamide staple fibre particle is formed by the aromatic polyamide staple fibre conjunction sth. made by twisting of more than 2 strands, and comprises the rubber between the aromatic polyamide staple fibre penetrating into described twisting.Described aromatic polyamide staple fibre, by more than 2 strands, is preferably 2 to 10 strands, and more preferably the aromatic polyamide fibre conjunction sth. made by twisting of 2 to 5 strands forms.
The rubber of described infiltration between the aromatic polyamide staple fibre of twisting is selected from the one in natural rubber, synthetic rubber and their combination.Identical to the explanation of crude rubber with above-mentioned for described natural rubber or elastomeric explanation, do not repeat them here.The rubber of described infiltration between the aromatic polyamide staple fibre of twisting preferably composition congruent with above-mentioned raw materials rubber phase, but the present invention is not limited to this.
The rubber of described infiltration between the aromatic polyamide staple fibre of twisting, can be positioned at the space of the central part of the aromatic polyamide staple fibre of described twisting, also can the multiply aromatic polyamide staple fibre surface of described twisting concavo-convex between.
Described aromatic polyamide staple fibre particle is with after the aromatic polyamide staple fibre conjunction sth. made by twisting of more than 2 strands, between the aromatic polyamide staple fibre of described twisting, permeate rubber combination and manufacture, or the aromatic polyamide staple fibre of described twisting is immersed in rubber combination manufactures, or TR thin rubber bar is positioned at center, in the mode being wound around described India-rubber strip, described aromatic polyamide staple fibre closed sth. made by twisting and manufacture.
Described aromatic polyamide staple fibre Particle Phase, for described aromatic polyamide staple fibre 100 weight part, comprises 10 to 50 weight parts, preferably comprises the rubber of the described infiltration of 30 to 40 weight parts.When the rubber content of described infiltration is less than 10 weight part, likely enter the problem of air; During more than 50 weight part, likely there is the problem be separated from each other between staple fibre.
The mean length of described aromatic polyamide staple fibre is 1 to 10mm, mean diameter is 0.01 to 1.0mm, and preferred mean length is 4 to 5mm, mean diameter is 0.1 to 0.15mm.When the mean length of described aromatic polyamide staple fibre is less than 1mm, the rubber content being wound around described aromatic polyamide staple fibre may be not enough; During more than 10mm, between described aromatic polyamide staple fibre and rubber, there is unbonded problem.In addition, when the mean diameter of described aromatic polyamide staple fibre is less than 0.01mm, described aromatic polyamide staple fibre ruptures due to undercapacity; During more than 1.0mm, the amount of winding of strips cord (belt cord) can be not enough.
Relative to crude rubber described in 100 weight parts, comprise 0.01 to 10 weight part, preferably comprise the described aromatic polyamide staple fibre particle of 0.05 to 5.5 weight part.When described aromatic polyamide staple fibre granule content is less than 0.01 weight part, the rigidity of belt laminating rubber can decline; During more than 10 weight part, belt laminating rubber may chap.
Described aromatic polyamide staple fibre can carry out surface treatment with the compound represented by following chemical formula 1 or its hydrate and polysulfide.
Use the compound that represented by described chemical formula 1 or its hydrate and polysulfide surface-treated aromatic polyamide staple fibre very excellent to the dispersiveness of rubber, therefore be evenly distributed in whole belt laminating rubber, can coating thickness be reduced thus.
Described aromatic polyamide staple fibre can by using the compound or its hydrate and described polysulfide mixing manufacture surface processing solution that are represented by above-mentioned chemical formula 1, the surface processing solution of described manufacture is coated on described aromatic polyamide staple fibre, or described aromatic polyamide staple fibre is immersed in described surface processing solution and manufactures.In addition, it by after aromatic polyamide fibre is carried out surface treatment, can block and manufactures, or carry out surface treatment after being blocked by described aromatic polyamide fibre and manufacture by described surface-treated aromatic polyamide staple fibre.
[chemical formula 1]
In above-mentioned chemical formula 1, described Me is basic metal, such as can is sodium or potassium, is preferably sodium.
Described n is the integer of 1 to 10, and described m is the integer of 1 to 6.
The compound that above-mentioned chemical formula 1 represents can use the form of hydrate or dihydrate.
Described polysulfide can be selected from the one in the compound of following chemical formula 2 to 6 expression.
[chemical formula 2]
[chemical formula 3]
[chemical formula 4]
[chemical formula 5]
[chemical formula 6]
In above-mentioned chemical formula 2 to 6, described R
1and R
2can be selected from the one in the aralkyl of hydrogen, halogen, nitro, hydroxyl, the alkyl of carbonatoms 1 to 12, the alkoxyl group of carbonatoms 1 to 12 and carbonatoms 1 to 12 independently of one another, be preferably hydrogen or alkyl.
Described m is the integer of 1 to 6, is preferably the integer of 1 to 4.
Described surface-treated aromatic polyamide staple fibre is relative to described aromatic polyamide staple fibre 100 weight part, use 1 to 2 weight part, preferably the compound represented by above-mentioned chemical formula 1 of 1.55 to 1.65 weight parts or the described polysulfide of its hydrate and 1 to 2 weight part, preferably 1.45 to 1.55 weight parts carry out surface treatment.
The compound that above-mentioned chemical formula 1 represents is used for surface-treated content, and relative to described aromatic polyamide staple fibre 100 weight part, during less than 1 weight part, described aromatic polyamide staple fibre cannot be evenly distributed in rubber; During more than 2 weight part, cannot described aromatic polyamide staple fibre be twisted a branch of.In addition, described polysulfide is used for surface-treated content, and relative to described aromatic polyamide staple fibre 100 weight part, during less than 1 weight part, described aromatic polyamide staple fibre cannot be uniformly distributed son in rubber; During more than 2 weight part, cannot described aromatic polyamide staple fibre be twisted a branch of.
Described tire belt laminating rubber combination can comprise silicon-dioxide further as weighting agent.Described silicon-dioxide can be N2 adsorption specific surface area (N
2sA) be 100 to 200m
2/ g, CTAB (cetyl trimethylammonium bromide) adsorption specific surface area is 100 to 200m
2/ g, but the present invention is not limited to this.
The N2 adsorption specific surface area of described silicon-dioxide is less than 100m
2/ g, is unfavorable for the reinforcing property of the silicon-dioxide as weighting agent; More than 200m
2/ g, is unfavorable for the processibility of rubber combination.In addition, the CTAB adsorption specific surface area of described silicon-dioxide is less than 100m
2/ g, is unfavorable for the reinforcing property of silicon-dioxide; More than 200m
2/ g, is unfavorable for the processibility of rubber combination.
Described silicon-dioxide, relative to described crude rubber 100 weight part, can comprise 20 to 90 weight parts, preferably comprise 30 to 70 weight parts, more preferably comprise 40 to 60 weight parts.Described silicon-dioxide containing quantity not sufficient 20 weight part time, the intensity of rubber improves may be not enough; When the content of described silicon-dioxide is more than 90 weight part, can there is crack (crack) in rubber.
Described tire belt laminating rubber combination optionally can also comprise the various additives such as vulcanizing agent, vulcanization accelerator, vulcanization accelerator additive, other weighting agents, coupling agent, protective agent, tenderizer or tackiness agent.All can use as long as described various additive this area is normally used, their content according to the proportioning used in common tire belt laminating rubber combination, can not be particularly limited.
Described vulcanizing agent preferably uses sulphur class vulcanizing agent.Described sulphur class vulcanizing agent can use the inorganic sulfur agents such as powder-sulphur (S), insoluble sulfur (S), sedimentation Sulfur (S), colloid sulphur and, the organic sulfurizing agents such as tetramethyl-thiuram disulfide (TMTD), tetraethylthiuram disulfide (TETD), dithio morpholine (dithiodimorpholine).Described sulphur class vulcanizing agent can use primary sulfur maybe can produce the sulphonating agent of sulphur particularly, such as, and amine disulphide (aminedisulfide), polymer sulphur etc.
Described vulcanizing agent, relative to crude rubber described in 100 weight parts, preferably comprises 0.5 to 4.0 weight part, can obtain applicable to add sulphur effect, and fewer responsive and obtain chemical stability to heat to make crude rubber.
Described vulcanization accelerator refers to and promotes to add sulphur speed or add the promotor (accelerator) that the sulphur stage plays promotion delayed action in the early stage.
Described vulcanization accelerator can use the one be selected from sulfenamide, thiazoles, thiurams, Thiourea, guanidine class, dithiocarbamate(s), aldehyde amines, aldehyde ammonia class, imidazolines, xanthogenic acid salt and their combination.
Described sulfenamide vulcanization accelerator can use and be selected from N cyclohexyl 2 benzothiazole sulfenamide (CBS), N tert butyl benzothiazole 2 sulfenamide (TBBS), N, a kind of sulphenamide compounds in N-dicyclohexyl-2-[4-morpholinodithio sulphenamide, N oxydiethylene 2 benzothiazole sulfenamide (N-oxydiethylene-2-benzothiazole sulfonamide), N, N-di-isopropyl-2-[4-morpholinodithio sulphenamide and their combination.
Described thiazoles vulcanization accelerator can use and be selected from 2-mercaptobenzothiazole (MBT), dithio-bis-benzothiazole (MBTS), the sodium salt of 2-mercaptobenzothiazole, the zinc salt of 2-mercaptobenzothiazole, the mantoquita of 2-mercaptobenzothiazole, the cyclohexyl amine salt of 2-mercaptobenzothiazole, 2-(2,4-dinitrophenyl) mercaptobenzothiazole, 2-(2,6-diethyl 4-morpholinothio) benzothiazole { a kind of thiazole compound in 2-(2,6-diethyl-4-morpholinothio) benzothiazole} and their combination.
Described thiurams vulcanization accelerator can use by tetramethyl thiuram disulfide (TMTD), Thiuram disulphide, tetra methylthiuram monosulphide, two pentamethylene thiuram disulfides (dipentamethylenethiuram disulfide), two pentamethylene thiuram monosulphide, two pentamethylene thiuram tetrasulfide, two pentamethylene thiuram hexasulfide, tetrabutyl thiuram disulfides, a kind of thiuram compound in pentamethylene thiuram tetrasulfide (pentamethylenethiuramtetrasulfide) and their combination.
Described Thiourea vulcanization accelerator can use a kind of thiourea be selected from thiocarbamide, diethyl thiourea, dibutyl thiourea, trimethyl thiourea, di-o-tolyl-thiourea and their combination.
Described guanidine class vulcanization accelerator can use a kind of guanidine class be selected from vulkacit D, di-o-tolylguanidine, triphenyl guanidine, adjacent toluene biguanides, vulkacit D phthalic ester (Diphenylguanidine phthalate) and their combination.
Described dithiocarbamate(s) vulcanization accelerator is selected from zinc-ethylphenyl dithiocarbamate, butyl phenyl zinc dithiocarbamate, Sodium dimethyldithiocarbamate 40min, ziram, zinc diethyldithiocarbamate, zinc dibutyl dithiocarbamate, zinc diamyldithiocarbamate, dipropyl disulfide is for carbaminate, the double salt of zinc pentamethylene dithiocarbamate (Zinc pentamethylenedithiocarbamate) and piperidines, hexadecyl sec.-propyl zinc dithiocarbamate, zinc octadecylisopropyldithiocarbamate, zinc dibenzyldithiocarbamate, Thiocarb, pentamethylene dithiocarbamic acid piperidines (Piperidine pentamethylenedithiocarbamate), Selenium dimethyl dithiocarbamate, tellurium diethyl dithiocarbamate, a kind of dithiocarbamate(s) compound in diamyl dithiocarbamate cadmium and their combination.
Described aldehyde amines or aldehyde ammonia class vulcanization accelerator can use and be selected from a kind of aldehyde amines in acetaldehyde-aniline reaction thing, butyl aldehyde aniline condensation product, vulkacit H (hexamethylenetetramine), acetaldehyde-ammonia react thing and their combination or aldehyde ammonia compounds.
Described imidazolines vulcanization accelerator can use the imidazolines such as 2-mercaptoimidazoline, and described xanthogenic acid salt vulcanization accelerator can use the xanthogenate compounds such as dibutyl xanthogenic acid zinc.
Boost productivity in order to the promotion by adding sulphur speed and improve rubber physical performance as far as possible, relative to described crude rubber 100 weight part, comprising the described vulcanization accelerator of 0.5 to 4.0 weight part.
Described vulcanization accelerator additive share the Synergist S-421 95 that its facilitation effect is used more completely, can use the one be selected from mineral-type vulcanization accelerator additive, organic vulcanization accelerator additive and their combination.
Described mineral-type vulcanization accelerator additive can use the one be selected from zinc oxide (ZnO), zinc carbonate, magnesium oxide (MgO), plumbous oxide, potassium hydroxide and their combination.Described organic vulcanization accelerator additive can use the one be selected from stearic acid, Zinic stearas, palmitinic acid, linolic acid, oleic acid, lauric acid, dibutyl ammonium oleate (dibutyl ammonium oleate), their derivative and their combination.
Particularly, can use described zinc oxide and described stearic acid as described vulcanization accelerator additive, now described zinc oxide is dissolved in described stearic acid simultaneously, forms effective mixture with described vulcanization accelerator, generate favourable sulphur in vulcanization reaction, make the polyreaction of rubber become easy.
When using described zinc oxide and described stearic acid, in order to play the effect of suitable vulcanization accelerator additive simultaneously, relative to crude rubber 100 weight part, described zinc oxide and described stearic acid use 1 to 5 weight part and 0.5 to 3 weight part respectively.When described zinc oxide and described stearic scope above-mentioned containing quantity not sufficient, vulcanization rate is slow and cause productivity to reduce; When exceeding above-mentioned scope, there is incipient scorch phenomenon and cause physical property to reduce.
Described tire belt laminating rubber combination can comprise weighting agent further.Described weighting agent can be selected from the one in carbon black, calcium carbonate, clay (hydrated aluminium silicate), aluminium hydroxide, xylogen, silicate, talcum and their combination.
N2 adsorption specific surface area (nitrogen surface area per gram, the N of described carbon black
2sA) be 30 to 300m
2oil number is 60 to 180cc/100g for/g, DBP (phthalic acid di tert butyl carbonate), but the present invention is not limited to this.
The N2 adsorption specific surface area of described carbon black is more than 300m
2during/g, be unfavorable for the processibility of rubber composition for tire; Less than 30m
2during/g, be unfavorable for the reinforcing property that weighting agent carbon black causes.In addition, when the DBP oil number of described carbon black is more than 180cc/100g, the processibility of rubber combination can reduce; During less than 60cc/100g, be unfavorable for the reinforcing property that carbon black causes.
The representational example of described carbon black has N110, N121, N134, N220, N231, N234, N242, N293, N299, S315, N326, N330, N332, N339, N343, N347, N351, N358, N375, N539, N550, N582, N630, N642, N650, N683, N754, N762, N765, N774, N787, N907, N908, N990 or N991 etc.
Described carbon black, relative to described crude rubber 100 weight part, comprises 30 to 80 weight parts, is preferably 45 to 65 weight parts, is more preferably 53 to 57 weight parts.Described carbon black containing quantity not sufficient 30 weight part, the reinforcing property that weighting agent carbon black causes declines; More than 80 weight parts, be unfavorable for the processing characteristics of described rubber combination.
Described coupling agent can use the one be selected from silicon sulfide hydride compounds, mercaptosilane compound, vinyl silane compound, amino silane compounds, glycidoxy silane compound, nitro silane compound, chlorinated silane compound, methacryl silanes compound and their combination.
Described silicon sulfide hydride compounds can be selected from two (3-triethoxysilylpropyl) tetrasulfide (bis (3-triethoxysilylpropyl) tetrasulfide), two (2-triethoxy silica ethyl) tetrasulfide, two (4-triethoxysilicane butyl) tetrasulfide, two (3-trimethoxy silicon propyl group) tetrasulfide, two (2-trimethoxy silica ethyl) tetrasulfide, two (4-trimethoxy silicon butyl) tetrasulfide, two (3-triethoxysilylpropyl) trisulphide, two (2-triethoxy silica ethyl) trisulphide, two (4-triethoxysilicane butyl) trisulphide, two (3-trimethoxy silicon propyl group) trisulphide, two (2-trimethoxy silica ethyl) trisulphide, two (4-trimethoxy silicon butyl) trisulphide, two (3-triethoxysilylpropyl) disulphide, two (2-triethoxy silica ethyl) disulphide, two (4-triethoxysilicane butyl) disulphide, two (3-trimethoxy silicon propyl group) disulphide, two (2-trimethoxy silica ethyl) disulphide, two (4-trimethoxy silicon butyl) disulphide, 3-trimethoxy silicon propyl group-N, N-dimethylamino thiocarbonyl group tetrasulfide (3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide), 3-triethoxysilylpropyl-N, N-dimethylamino thiocarbonyl group tetrasulfide, 2-triethoxy silica ethyl-N, N-dimethylamino thiocarbonyl group tetrasulfide, 2-trimethoxy silica ethyl-N, N-dimethylamino thiocarbonyl group tetrasulfide, 3-trimethoxy silicon propylbenzene benzothiazolyl tetrasulfide (3-trimethoxysilylpropylbenzothiazolyltetrasulfide), 3-triethoxysilylpropyl benzothiazole tetrasulfide, 3-trimethoxy silicon propyl methacrylate monosulphide, one in 3-trimethoxy silicon propyl methacrylate monosulphide and their combination.
Described mercaptosilane compound is selected from the one in 3-mercaptopropyi Trimethoxy silane, 3-Mercaptopropyltriethoxysilane, 2-mercaptoethyl Trimethoxy silane, 2-mercaptoethyl triethoxyl silane and their combination.Described ethene system coupling agent can be selected from the one in Ethoxysilane, vinyltrimethoxy silane and their combination.Described amine coupling agent can be selected from the one in APTES, 3-TSL 8330,3-(2-amino-ethyl) aminopropyltriethoxywerene werene, 3-(2-amino-ethyl) TSL 8330 and their combination.
Described glycidoxy silane compound can be selected from the one in γ-glycidoxypropyl group triethoxyl silane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxypropyl diethoxy silane, γ-glycidoxypropyl dimethoxysilane and their combination.Described nitro silane compound can use the one be selected from 3-nitropropyl Trimethoxy silane, 3-nitropropyltriethoxysilane and their combination.Described chlorinated compound system coupling agent can be selected from the one in 3-r-chloropropyl trimethoxyl silane, 3-chloropropyl triethoxysilane, 2-chloroethyl Trimethoxy silane, 2-chloroethyl triethoxyl silane and their combination.
Described methacryl silanes compound can be selected from the one in γ-methacryloxypropyl trimethoxy silane, γ-methacryloyloxypropyl methyl dimethoxysilane, γ-methacryloxypropyl dimethyl methoxy silane and their combination.
In order to the dispersiveness of described silicon-dioxide, relative to described crude rubber 100 weight part, comprise the described coupling agent of 1 to 20 weight part.Described coupling agent containing quantity not sufficient 1 weight part time, the dispersiveness of described silicon-dioxide improves not enough, and the processibility of rubber reduces or low fuel consumption performance reduces; During more than 20 weight part, the interaction of silicon-dioxide and rubber is too strong, although low fuel consumption excellent performance, braking ability can reduce a lot.
Described tenderizer easily processes to give rubber plasticity-or reduce the hardness of vulcanized rubber and add in rubber combination, other oil like material used when referring to rubber formulation or when manufacturing.Described tenderizer refer to technical oil (Process oil) or other be included in oils in rubber combination.Described tenderizer can use the one be selected from petroleum-type oil, Vegetable oil lipoprotein and their combination, but the present invention is not limited to this.
Described petroleum-type oil can use the one be selected from paraffin class oil, naphthenic oil, fragrant same clan oil and their combination.
P-1, P-2, P-3, P-4, P-5, P-6 etc. of representative example You Meichang Co., Ltd. of described paraffin class oil, the N-1 of representative example You Meichang Co., Ltd. of described naphthenic oil, N-2, N-3, A-2, A-3 etc. of representative example You Meichang Co., Ltd. of described fragrant same clan oil.
But, recently along with people are to the lifting of Environmental awareness, polynuclear aromatics (Polycyclic Aromatic Hydrocarbons contained in known described fragrant same clan oil, hereinafter referred to as " PAHs ") content when being more than 3 % by weight, the possibility of bringing out cancer is high, therefore TDAE (environment-friendly aromatic oil is preferably used, treated distillate aromatic extract) oil, MES (appropriate extraction solvent compound, mildextraction solvate) oil, RAE (residual aromatic extract) oil or heavy naphthenic oil.
Particularly, the oil used as described tenderizer preferably uses the total amount relative to described oil, the total content of PAHs composition is less than 3 % by weight, dynamic viscosity is that the aromatic component in more than 95 (210 ℉ SUS), tenderizer is 15 to 25 % by weight, naphthenic composition be 27 to 37 % by weight and paraffin class composition be 38 to 58 % by weight TDAE oil.
Described TDAE oil can make cold property, the fuel consumption excellent performance of the tire comprising described TDAE oil, also has to bring out the also favourable characteristic of the environmental factorss such as cancer possibility to PAHs simultaneously.
Described Vegetable oil lipoprotein can use the one be selected from Semen Ricini oil, Oleum Gossypii semen, Semen Lini oil, Canola oil, soybean oil, plam oil, Oleum Cocois, peanut oil, pine-tree oil, Stockholm tar, Yatall MA, Semen Maydis oil, Rice pollard oil, Thistle oil, sesame oil, sweet oil, sunflower seed oil, palm-nut oil, Camellia oil, jojoba oil, macadimia nut oil, Thistle oil, tung oil and their combination.
Preferably relative to described crude rubber 100 weight part, use the described tenderizer of 0 to 150 weight part, be conducive to the processibility of crude rubber.
Described tire belt laminating rubber combination manufactures by common 2 step continuously manufacturings.Namely, by at the maximum temperature of 110 to 190 DEG C, preferably carry out thermo-mechanical processi or mixing first step at the high temperature of 130 to 180 DEG C, and during the ending phase of cross-link bond system mixing, typically lower than 110 DEG C, such as carry out the second step of mechanical treatment at 40 to 100 DEG C of low temperature, manufacture in suitable mixing machine and form, but the present invention is not limited to this.
Described tire belt laminating rubber combination is not limited to tire belt portion, can be included in the multiple rubber integrant forming tire.Described rubber integrant has tyre surface (tread cap and tread base), tyre sidewall, sidewall insert, tyre bead summit glue (apex), chafer fabric (chafer), steel bead wire cover or inside tires liner etc.
Tire according to another embodiment of the present invention utilizes described tire belt laminating rubber combination to manufacture.As long as utilize the method for described tire belt laminating rubber combination manufacture tire can use for the method for existing Tire production, the present invention is not repeating this.
Described tire can be passenger car tire, contest tire, aircraft tire, farm machinery tire, engineering machinery tire, card tire for vehicles or bus tire etc.In addition, described tire can be meridian (radial) tire or oblique (bias) tire, preferred radial.
Tire belt laminating rubber combination of the present invention improves the rigidity of belt laminating rubber, reduces coating thickness, reduces the lag-effect of described belt laminating rubber, thus the power loss occurred when can reduce tire rotation.
Embodiment
Below, in order to those skilled in the art easily implement the present invention, embodiments of the invention are described in detail.But the present invention may be embodied as various different form, is not limited to described herein
Embodiment.
[Production Example: the manufacture of rubber combination]
The composition of following table 1 is utilized to manufacture the tire belt laminating rubber combination of embodiment and comparative example.The manufacture of described rubber combination is according to the manufacture method of common rubber combination.
[table 1]
(1) the 1st crude rubber: solution styrene-divinyl rubber.
(2) the 2nd crude rubbers: divinyl rubber.
(3) silicon-dioxide: N2 adsorption specific surface area is 150m
2/ g, CTAB adsorption specific surface area are 150m
2/ g.
(4) oil: the oil with ozone resistants feature.
(5) aromatic polyamide staple fibre particle: (mean length is 4mm by 3 strands of aromatic polyamide staple fibres, mean diameter is 0.125mm, relative to aromatic polyamide staple fibre 100 weight part, (Me is Na to the compound represented with described chemical formula 1, m is 1, n is 6) dihydrate 1.6 weight part and described chemical formula 6 represent compound (R
1and R
2for hydrogen, m is 2) 1.5 weight parts carry out surface treatment) after twisting, between the aromatic polyamide staple fibre of described twisting, permeate the rubber (solution styrene-divinyl rubber) of 35 weight parts and obtain.
[experimental example: the physical property measurement of the rubber combination of manufacture]
Physical property measurement is carried out to the rubber test piece manufactured in above-described embodiment and comparative example, and its result has been illustrated in table 2.
-hardness is with shore A(Shore A) sclerometer carries out the result that measures.Hardness is the value representing operational stability, and its value more high stability of operation is more excellent.
-100% and 300% modulus (kgf/m
2): modulus (Modulus) for elongation 100% or 300% time tensile strength, measure according to ISO37 specification, numerical value higher expression intensity is more excellent.
-abrasion vector (g): abrasion vector is blue Berne stage of wear (Lambourn abrasiontester), represent when rotating under normal temperature, sliding rate 25%, load 1.5kg, the numerical value of the loss amount of the rubber of abrasion, the larger wear hardness of its numerical value is more excellent.
-tan δ utilizes ARES (10Hz, 0.5% stress) to measure, and 60 DEG C of tan δ rotate impedance numerical value more low being more conducive to, and 0 DEG C of tan δ is that the higher braking ability of numerical value is more excellent.
[table 2]
| Comparative example 1 | Embodiment 1 | Embodiment 2 | |
| Hardness | 69 | 71 | 72 |
| 100% modulus | 8.23 | 9.29 | 9.99 |
| 300% modulus | 121.3 | 139.2 | 144.3 |
| Blue Berne abrasion vector | 1.009 | 0.799 | 0.891 |
| 0℃Tanδ | 0.280 | 0.305 | 0.335 |
| 60℃Tanδ | 0.102 | 0.098 | 0.098 |
Known with reference to upper table 2, embodiment 1 is with 2 compared with comparative example 1, and when not having the loss of wear hardness and rotation impedance, braking ability improves greatly.Thus can know that described aromatic polyamide staple fibre particle can improve the rigidity of belt when adding in belt laminating rubber combination.
Above preferred embodiment of the present invention is described in detail; but protection scope of the present invention does not limit thus, the various distortion utilizing the those skilled in the art of the key concept of the present invention defined in following claims to do and improvement kenel all fall into protection scope of the present invention.
Claims (4)
1. tire belt laminating rubber combination, it comprises:
The crude rubber of 100 weight parts;
The aromatic polyamide staple fibre particle of 0.01 to 10 weight part, it is formed by the aromatic polyamide staple fibre conjunction sth. made by twisting of more than 2 strands, and comprise the rubber of infiltration between the described aromatic polyamide staple fibre of twisting, wherein, described aromatic polyamide staple fibre Particle Phase is for described aromatic polyamide staple fibre 100 weight part, comprise the rubber of the described infiltration of 10 to 50 weight parts, described aromatic polyamide staple fibre is mean length is 1 to 10mm, mean diameter is 0.01 to 1.0mm, wherein
Described aromatic polyamide staple fibre uses the compound or its hydrate that are represented by following chemical formula 1 and polysulfide to carry out surface treatment,
In described chemical formula 1, described Me is basic metal, and described n is the integer of 1 to 10, and described m is the integer of 1 to 6.
2. tire belt laminating rubber combination according to claim 1, wherein, described polysulfide is selected from the one in the compound of following chemical formula 2 to 6 expression,
In above-mentioned chemical formula 2 to 6, described R
1and R
2be selected from the one in the aralkyl of hydrogen, halogen, nitro, hydroxyl, the alkyl of carbonatoms 1 to 12, the alkoxyl group of carbonatoms 1 to 12 and carbonatoms 1 to 12 independently of one another, described m is the integer of 1 to 6.
3. tire belt laminating rubber combination according to claim 1, wherein, it is 100 to 200m that described tire belt laminating rubber combination comprises N2 adsorption specific surface area further
2/ g, CTAB (cetyl trimethylammonium bromide) adsorption specific surface area is 100 to 200m
2silicon-dioxide 20 to 90 weight part of/g.
4. a tire, utilizes the tire belt laminating rubber combination in claim 1 to 3 described in any one to manufacture.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2011-0144831 | 2011-12-28 | ||
| KR1020110144831A KR101440099B1 (en) | 2011-12-28 | 2011-12-28 | Rubber composition for tire belt topping and tire manufactured by using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103183853A CN103183853A (en) | 2013-07-03 |
| CN103183853B true CN103183853B (en) | 2015-08-05 |
Family
ID=48675314
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210570424.2A Expired - Fee Related CN103183853B (en) | 2011-12-28 | 2012-12-25 | Tire belt laminating rubber combination and the tire utilizing said composition to manufacture |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR101440099B1 (en) |
| CN (1) | CN103183853B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104292528A (en) * | 2013-07-18 | 2015-01-21 | 宁波大学 | High strength rubber and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1045611A (en) * | 1989-03-14 | 1990-09-26 | 纳幕尔杜邦公司 | High strength cored cord |
| CN1914258A (en) * | 2004-12-27 | 2007-02-14 | 横滨橡胶株式会社 | Masterbatch of rubber/short fiber, manufacturing method for the same and pneumatic tire using the same |
| CN1982088A (en) * | 2005-12-13 | 2007-06-20 | 住友橡胶工业株式会社 | Runflat tire |
| CN101120135A (en) * | 2005-02-18 | 2008-02-06 | 帝人特瓦隆有限公司 | Method for enhancing rubber properties by using Bunte salt-treated fiber |
| CN101305033A (en) * | 2005-10-10 | 2008-11-12 | 帝人芳纶有限公司 | Composition comprising sulfurized particle |
| CN101462467A (en) * | 2007-12-18 | 2009-06-24 | 固特异轮胎和橡胶公司 | Tire with component containing aramid fibers |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4532080A (en) | 1982-10-21 | 1985-07-30 | Monsanto Europe, S.A. | Adhesion promoters |
| JP4755488B2 (en) * | 2005-11-25 | 2011-08-24 | 住友ゴム工業株式会社 | Radial tires for motorcycles and band cords used therefor |
-
2011
- 2011-12-28 KR KR1020110144831A patent/KR101440099B1/en not_active IP Right Cessation
-
2012
- 2012-12-25 CN CN201210570424.2A patent/CN103183853B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1045611A (en) * | 1989-03-14 | 1990-09-26 | 纳幕尔杜邦公司 | High strength cored cord |
| CN1914258A (en) * | 2004-12-27 | 2007-02-14 | 横滨橡胶株式会社 | Masterbatch of rubber/short fiber, manufacturing method for the same and pneumatic tire using the same |
| CN101120135A (en) * | 2005-02-18 | 2008-02-06 | 帝人特瓦隆有限公司 | Method for enhancing rubber properties by using Bunte salt-treated fiber |
| CN101305033A (en) * | 2005-10-10 | 2008-11-12 | 帝人芳纶有限公司 | Composition comprising sulfurized particle |
| CN1982088A (en) * | 2005-12-13 | 2007-06-20 | 住友橡胶工业株式会社 | Runflat tire |
| CN101462467A (en) * | 2007-12-18 | 2009-06-24 | 固特异轮胎和橡胶公司 | Tire with component containing aramid fibers |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20130076302A (en) | 2013-07-08 |
| KR101440099B1 (en) | 2014-09-17 |
| CN103183853A (en) | 2013-07-03 |
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